Substituent effects on reactivity of 3-cinnamoylcoumarins with thiols of biological interest

Margarita E. Aliaga, William Tiznado, Bruce K. Cassels, Marco T. Nuñez, Daniela Millán, Edwin G. Pérez, Olimpo García-Beltrán, Paulina Pavez

Resultado de la investigación: Article

5 Citas (Scopus)

Resumen

The Michael addition reactions of the biothiols cysteine, homocysteine, cysteinyl-glycine, γ-glutamyl-cysteine and glutathione with 3-cinnamoylcoumarin derivatives (ChC1-ChC4) in aqueous solution (30 °C, ionic strength 0.2 M KCl) were followed fluorimetrically and evaluated kinetically. The study was completed with a theoretical analysis based on the inverse of the Fukui potential (1/νf (r)), which is proposed for the first time as a local softness descriptor. Thus, considering both experimental results and theoretical analysis, the following conclusions can be drawn: (i) the reactivity of the tested probes towards Michael addition increases in the para-substitution sequence: H < OEt < SMe < Br < NO2, and is not correlated with the σP values of the substituents; (ii) in turn, the descriptor proposed here as local softness (1/νf (r)) appears as a promising reactivity index that is able to explain the higher kN values found for both electron-withdrawing and electron-donating groups; (iii) the nucleophilic reactivity of the biothiols employed increases in the sequence Cys-Gly < Hcy < GSH < Cys < γ-Glu-Cys; and also finally (iv) we have demonstrated that these probes can be used for fluorimetric thiol determination in SH-SY5Y cells.

Idioma originalEnglish
Páginas (desde-hasta)697-704
Número de páginas8
PublicaciónRSC Advances
Volumen4
N.º2
DOI
EstadoPublished - 2014

Huella dactilar

Sulfhydryl Compounds
cysteinylglycine
Cysteine
Addition reactions
Electrons
Homocysteine
Ionic strength
Glutathione
Amino acids
Substitution reactions
Derivatives

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Chemistry(all)

Citar esto

Aliaga, M. E., Tiznado, W., Cassels, B. K., Nuñez, M. T., Millán, D., Pérez, E. G., ... Pavez, P. (2014). Substituent effects on reactivity of 3-cinnamoylcoumarins with thiols of biological interest. RSC Advances, 4(2), 697-704. https://doi.org/10.1039/c3ra44695f
Aliaga, Margarita E. ; Tiznado, William ; Cassels, Bruce K. ; Nuñez, Marco T. ; Millán, Daniela ; Pérez, Edwin G. ; García-Beltrán, Olimpo ; Pavez, Paulina. / Substituent effects on reactivity of 3-cinnamoylcoumarins with thiols of biological interest. En: RSC Advances. 2014 ; Vol. 4, N.º 2. pp. 697-704.
@article{c10d1a7a147c40ca8cd62f08ef779793,
title = "Substituent effects on reactivity of 3-cinnamoylcoumarins with thiols of biological interest",
abstract = "The Michael addition reactions of the biothiols cysteine, homocysteine, cysteinyl-glycine, γ-glutamyl-cysteine and glutathione with 3-cinnamoylcoumarin derivatives (ChC1-ChC4) in aqueous solution (30 °C, ionic strength 0.2 M KCl) were followed fluorimetrically and evaluated kinetically. The study was completed with a theoretical analysis based on the inverse of the Fukui potential (1/νf (r)), which is proposed for the first time as a local softness descriptor. Thus, considering both experimental results and theoretical analysis, the following conclusions can be drawn: (i) the reactivity of the tested probes towards Michael addition increases in the para-substitution sequence: H < OEt < SMe < Br < NO2, and is not correlated with the σP values of the substituents; (ii) in turn, the descriptor proposed here as local softness (1/νf (r)) appears as a promising reactivity index that is able to explain the higher kN values found for both electron-withdrawing and electron-donating groups; (iii) the nucleophilic reactivity of the biothiols employed increases in the sequence Cys-Gly < Hcy < GSH < Cys < γ-Glu-Cys; and also finally (iv) we have demonstrated that these probes can be used for fluorimetric thiol determination in SH-SY5Y cells.",
author = "Aliaga, {Margarita E.} and William Tiznado and Cassels, {Bruce K.} and Nu{\~n}ez, {Marco T.} and Daniela Mill{\'a}n and P{\'e}rez, {Edwin G.} and Olimpo Garc{\'i}a-Beltr{\'a}n and Paulina Pavez",
year = "2014",
doi = "10.1039/c3ra44695f",
language = "English",
volume = "4",
pages = "697--704",
journal = "RSC Advances",
issn = "2046-2069",
publisher = "Royal Society of Chemistry",
number = "2",

}

Aliaga, ME, Tiznado, W, Cassels, BK, Nuñez, MT, Millán, D, Pérez, EG, García-Beltrán, O & Pavez, P 2014, 'Substituent effects on reactivity of 3-cinnamoylcoumarins with thiols of biological interest', RSC Advances, vol. 4, n.º 2, pp. 697-704. https://doi.org/10.1039/c3ra44695f

Substituent effects on reactivity of 3-cinnamoylcoumarins with thiols of biological interest. / Aliaga, Margarita E.; Tiznado, William; Cassels, Bruce K.; Nuñez, Marco T.; Millán, Daniela; Pérez, Edwin G.; García-Beltrán, Olimpo; Pavez, Paulina.

En: RSC Advances, Vol. 4, N.º 2, 2014, p. 697-704.

Resultado de la investigación: Article

TY - JOUR

T1 - Substituent effects on reactivity of 3-cinnamoylcoumarins with thiols of biological interest

AU - Aliaga, Margarita E.

AU - Tiznado, William

AU - Cassels, Bruce K.

AU - Nuñez, Marco T.

AU - Millán, Daniela

AU - Pérez, Edwin G.

AU - García-Beltrán, Olimpo

AU - Pavez, Paulina

PY - 2014

Y1 - 2014

N2 - The Michael addition reactions of the biothiols cysteine, homocysteine, cysteinyl-glycine, γ-glutamyl-cysteine and glutathione with 3-cinnamoylcoumarin derivatives (ChC1-ChC4) in aqueous solution (30 °C, ionic strength 0.2 M KCl) were followed fluorimetrically and evaluated kinetically. The study was completed with a theoretical analysis based on the inverse of the Fukui potential (1/νf (r)), which is proposed for the first time as a local softness descriptor. Thus, considering both experimental results and theoretical analysis, the following conclusions can be drawn: (i) the reactivity of the tested probes towards Michael addition increases in the para-substitution sequence: H < OEt < SMe < Br < NO2, and is not correlated with the σP values of the substituents; (ii) in turn, the descriptor proposed here as local softness (1/νf (r)) appears as a promising reactivity index that is able to explain the higher kN values found for both electron-withdrawing and electron-donating groups; (iii) the nucleophilic reactivity of the biothiols employed increases in the sequence Cys-Gly < Hcy < GSH < Cys < γ-Glu-Cys; and also finally (iv) we have demonstrated that these probes can be used for fluorimetric thiol determination in SH-SY5Y cells.

AB - The Michael addition reactions of the biothiols cysteine, homocysteine, cysteinyl-glycine, γ-glutamyl-cysteine and glutathione with 3-cinnamoylcoumarin derivatives (ChC1-ChC4) in aqueous solution (30 °C, ionic strength 0.2 M KCl) were followed fluorimetrically and evaluated kinetically. The study was completed with a theoretical analysis based on the inverse of the Fukui potential (1/νf (r)), which is proposed for the first time as a local softness descriptor. Thus, considering both experimental results and theoretical analysis, the following conclusions can be drawn: (i) the reactivity of the tested probes towards Michael addition increases in the para-substitution sequence: H < OEt < SMe < Br < NO2, and is not correlated with the σP values of the substituents; (ii) in turn, the descriptor proposed here as local softness (1/νf (r)) appears as a promising reactivity index that is able to explain the higher kN values found for both electron-withdrawing and electron-donating groups; (iii) the nucleophilic reactivity of the biothiols employed increases in the sequence Cys-Gly < Hcy < GSH < Cys < γ-Glu-Cys; and also finally (iv) we have demonstrated that these probes can be used for fluorimetric thiol determination in SH-SY5Y cells.

UR - http://www.scopus.com/inward/record.url?scp=84889594278&partnerID=8YFLogxK

U2 - 10.1039/c3ra44695f

DO - 10.1039/c3ra44695f

M3 - Article

AN - SCOPUS:84889594278

VL - 4

SP - 697

EP - 704

JO - RSC Advances

JF - RSC Advances

SN - 2046-2069

IS - 2

ER -